Novel polyethers having terminal amino groups and plastic materials made therefrom

ABSTRACT

Polyurea polymer compositions produced by the isocyanate polyaddition process by reacting compounds having terminal groups and represented by the general formula: ##STR1## wherein z is an integer of 2 to 4, X is oxygen or sulfur and R is a group of the formula: 
     
         -Y-[Ar-B].sub.k 
    
     wherein k is an integer of 1 to 4, Ar is an aromatic group, Y is B when k is 1 and when k is 2, then Y is an alkylidene group having 1 to 5 carbon atoms and B represents a divalent polyalkylene ether group or polyalkylene thioether group such as is obtained by the removal of the hydroxyl or mercapto groups from a polyalkylene ether diol or a polyalkylene thioether diol of a molecular weight of about 100 to 15000, with a polyisocyanate. The polymer compositions are useful for the formation of vehicle tires of all types and for the formation of portions of vehicle wheels, for belts, fasteners and shoe soles.

REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.964,841, filed Nov. 29, 1978, which in turn is a division of applicationSer. No. 735,291, filed Oct. 26, 1976, now U.S. Pat. No. 4,129,741issued Dec. 12, 1978, the entire disclosure of which is relied onherein.

The invention relates to novel polyamines, their production and theiruse in the production of polyureas of increased thermal stability andimproved tensile and structural strength.

It is known that polyureas possess a number of considerable advantagesover polyurethanes of corresponding structure. Polyureas are obtained byreaction of polyisocyanates with polyamines. Suitable polyamines areparticularly polyether polyamines of higher molecular weight.

According to German Offenlegungsschrift No. 2,019,432, polyaminessuitable for the production of such polyureas are obtained fromaliphatic polyether polyols and isatoic acid anhydride.

It was found that the use of polyether polyamines having one or severalaromatic nuclei (rings) in their molecule (center) leads to theobtention of polyureas which are far superior to those known in respectto thermal stability and tensile and structural strength.

The invention relates to novel compounds having terminal amino groups,said novel compounds being of the general formula ##STR2## wherein z isan integer of 2 to 4, X is oxygen or sulfur and R is a group of theformula

    --Y--[Ar-B].sub.k                                          (II)

wherein k stands for an integer of 1 to 4, Ar is an aromatic group, Ywhen k=1 is B and when k=2 to 4 is an alkylidene group having 1 to 5carbon atoms and B represents a divalent polyalkylene ether group orpolyalkylene thioether group such as it is obtained by removing thehydroxyl or mercapto groups from a polyalkylene ether diol or apolyalkylene thioether dithiol of a molecular weight of about 100 to15000, in particular of about 500 to 3000.

A further object of the invention is the production of the novelcompounds of the formula I. It can be effected by heating of a polyetherpolyol or a polythioether polythiol of the formula III

    R(HX).sub.z                                                (III)

wherein R and X have the meanings defined above and z is an integer of 2to 4, with at least two equivalents of isatoic acid anhydride in thepresence of strong bases to temperatures of 30° to 150° C., preferablyof 45° to 130° C. The reaction can be carried out with or without thepresence of inert solvents. The amount of catalyst used can be variedwithin a wide range. Preferably, 1 to 10 parts by weight of the alkalinecompound per 100 parts by weight of isatoic acid anhydride are used. Thereaction is completed as soon as gas development ceases. The catalystand excess isatoic acid anhydride are filtered off, optionally afteraddition of an inert solvent, and the final product is obtained with ahigh degree of purity after treatment with CO₂, shaking with water anddrying in vacuo under stirring. For the majority of applicationpurposes, simple filtration of the amino polyether suffices.

Suitable starting materials for the process according to the inventionare polyols and polythiols of the formula III of a molecular weight ofabout 300 to 15000, preferably of about 400 to 10000 and in particularof about 500 to 3000, comprising polyether polyols and polyetherpolythiols or as well polyether segments or polythioether segments.

Preferred in the process according to the invention is the use ofpolymerisates obtained by the reaction of ethylene oxide, propyleneoxide or other 1,2-alkylene oxides with a compound corresponding to R inthe formula II wherein B=OH, CH₂ OH, OCH₂ --CH₂ --OH or CH₂ CH(CH₃)OH.Such compounds are produced according to generally known processes asdisclosed in U.S. Pat. No. 2,652,419.

Preferred are compounds, or is the production of compounds, of theformula I wherein Ar represents a p-phenylene group, further suchcompounds wherein Ar stands for a diphenyl alkane group.

Of these groups, the diphenyl propane (Bisphenol A) group is preferred.

In view of the multitude of application possibilities, compounds of theformula I, or their production, are (is) preferred wherein B representsa polyethylene ether group, a polypropylene ether group or polyalkyleneether group containing ethylene ether groups and propylene ether groupsin any given sequence.

B can further represent a group containing ether groups as well asthioether groups.

In view of the inexpensive obtention of the starting materials, it isfurther preferred to use compounds of the formula I, or, to produce suchcompounds, wherein B stands for a polyalkylene ether group derived fromtetrahydrofurane or a polyalkylene ether group containing ethylene ethergroups and alkylene ether groups derived from tetrahydrofurane in anygiven sequence, or for a polyalkylene ether group containing alkyleneether groups derived from tetrahydrofurane and propylene ether groups,in any given sequence.

Typical examples of the novel compounds having terminal amino groupsaccording to the invention or obtainable according to the invention,said compounds having the formula I, are the following: ##STR3##

In these formulae, the indices m and n in each case represent suchintegers that molecular weights of about 100 to 15000, in particular of500 to 3000, result in the compounds obtained. A further object of theinvention is the application of the new compounds of the formula I asreactants with polyisocyanates in the production of plastic materialsaccording to the isocyanate polyaddition process.

The production of plastic materials from the compounds according to theinvention or obtainable according to the invention according to theisocyanate polyaddition process can be effected in any manner known inpolyurethane chemistry, i.e. for the reaction of polyhydroxyl compoundswith polyisocyanates. This means that the reaction of the new compoundswith polyisocyanates can be carried out in the presence of all theadditives known in polyurethane chemistry, such as catalysts,flame-retarding substances, and the like.

In the production of elastomeric plastic materials of a high modulus ofelasticity, the polyadducts have up to now preferably been formed in thepresence of low molecular aromatic diamines as chain extenders. Sincethese diamines are carcinogenic, there exist objections of aphysiological nature to their use. When employing the compoundsaccording to the invention in the production of elastomeric plasticmaterials of a high modulus of elasticity, the presence of low moleculararomatic diamines can be omitted.

Suitable polyisocyanates in the production of the polyadducts by meansof the new compounds according to the invention are all polyisocyanatesknown in polyurethane chemistry, such as, for instance, tetramethylenediisocyanate, hexamethylene diisocyanate, 2,4-diisocyanatotoluene,2,6-diisocyanatotoluene, mixtures of these isomers,4,4-diisocyanatodiphenyl methane and the like.

As already mentioned, the polyadducts produced employing the compoundsaccording to the invention or obtainable according to the invention arefar superior to polyurethanes of corresponding structure due to a numberof striking advantages, such as, in particular, stability, thermalstability, abrasion and wear resistance and elasticity.

The production of the compounds of the formula I is explained by meansof the following Examples:

EXAMPLE 1

124.8 g (0.1 mol) of a compound of the formula ##STR4## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 2.5 g powdered sodiumhydroxide are heated for 3 hours to 80° C. and then for 15 minutes to100° C. After cooling, 150 ml methylene chloride are added to themixture and it is filtered. Then, 200 ml water are added to the filtrateand CO₂ is introduced in order to completely remove the sodiumhydroxide. This is followed by three extractions with 200 ml water eachand concentration in vacuo of the organic phase. The yield obtainedamounts to 147.6 g (97% of the theory, which means that 97% of theOH-groups have reacted with the isatic acid) of a honey-coloured,viscous substance.

Amine titration: for 1.7462 g substance: 23.0 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 2

145.2 g (0.2 mol) of a compound of the formula ##STR5## wherein m and nare integers, 71.8 g of isatoic acid anhydride and 3 g powdered sodiumhydroxide are reacted and treated as described in Example 1. Thisprocedure yields 177.4 g (92% of the theory) of a honey-coloured, highlyviscous substance.

Amine titration: for 1.2561 g substance: 26.1 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 3

173.6 g (0.1 mol) of a compound of the formula ##STR6## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 2.0 g powdered sodiumhydroxide are heated for 4 hours to 75° C. and then for 30 minutes to100° C. and treated in analogy to Example 1. This procedure yields 187.5g (95% of the theory) of a honey-coloured, viscous substance.

Amine titration: for 2.6579 g substance: 27.1 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 4

174.4 g (0.1 mol) of a compound of the formula ##STR7## wherein m and nare integers, 35.9 g isatoic acid anhydride and 2.5 g powdered sodiumhydroxide are reacted and treated according to Example 1. This procedureyields 180.4 g (91% of the theory) of a honey-coloured, viscoussubstance.

Amine titration: for 2.4732 g substance: 25.0 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 5

905 g (0.1 mol) of a compound of the formula ##STR8## wherein n is aninteger, 35.9 g of isatoic acid anhydride and 7 g powdered sodiumhydroxide are heated for 4 hours to 80° C. and then for 1 hour to 100°C. and treated in analogy to Example 1. This procedure yields 871 g (95%of the theory) of a honey-coloured, viscous substance.

Amine titration: for 4.8358 g substance: 9.6 ml 0.1 n HClO₄ in glacialacetic acid (89% of the theory), which means that 89% of all OH-groupshave reacted with isatic acid anhydride.

EXAMPLE 6

1400 g (0.1 mol) of a compound of the formula ##STR9## wherein n is aninteger, 35.9 g isatoic acid anhydride and 15 g powdered sodiumhydroxide are reacted according to Example 5. The yield amounts to 121 g(85% of the theory) of a honey-coloured, viscous substance.

Amine titration: for 7.723 g substance: 9.0 ml 0.1 n HClO₄ in glacialacetic acid (83% of the theory), which means that 83% of all OH-groupshave reacted with isatic acid anhydride.

EXAMPLE 7

176 g (0.1 mol) of a compound of the formula ##STR10## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 5.0 g powdered sodiumhydroxide are heated first for 4 hours to 80° C. and then for 1 hour to100° C. and treated in analogy to Example 1. The yield amounts to 189.5g (95% of the theory) of a honey-coloured, viscous substance.

Amine titration: for 2.194 g substance: 22 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 8

139 g (0.1 mol) of a compound of the formula ##STR11## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 5.0 g powdered sodiumhydroxide are reacted and treated as described in Example 7. Thisprocedure yields 153.4 g (94% of the theory) of a honey-coloured,viscous substance.

Amine titration: for 1.7416 g substance: 21.2 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 9

195.6 g (0.1 mol) of a compound of the formula ##STR12## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 3.0 g powdered sodiumhydroxide are heated for 3 hours to 75° C. and for 15 minutes to 100° C.After cooling, 150 ml methylene chloride are added to the mixture and itis filtered. Then, 200 ml water are added to the filtrate and CO₂ isintroduced, in order to completely remove the sodium hydroxide. Afterthree extractions with 200 ml water each, the organic phase isconcentrated in vacuo. This procedure yields 194.7 g (93% of the theory)of a honey-coloured, viscous substance.

Amine titration: for 1.8263 g substance: 17.6 ml 0.1 n HClO₄ in glacialacetic acid.

EXAMPLE 10

140.6 g (0.1 mol) of a compound of the formula ##STR13## wherein m and nare integers, 35.9 g of isatoic acid anhydride and 2.5 g powdered sodiumhydroxide are reacted and treated according to Example 9. This procedureyields 157.8 g (96% of the theory) of a honey-coloured, viscoussubstance.

Amine titration: for 1.5172 g substance: 18.6 ml 0.1 n HClO₄ in glacialacetic acid.

The following Examples cover the application of the compounds of theformula I:

EXAMPLE 11

152.2 g (0.1 mol) of the diamine produced in Example 1 and 18.5 gtoluylene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) are mixed,poured into a mould and then first heated for 1 hour to 60° C. and thenfor 24 hours to 100° C. This procedure yields an elastomer of excellentmechanical properties.

    ______________________________________                                        Tensile strength:  280 kp cm.sup.-2                                           Structural strength:                                                                             50 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         60                                                         ______________________________________                                    

EXAMPLE 12

192.8 g (0.2 mol) of the diamine produced in Example 2 and 37 gtoluylene diisocyanate are heated in a mould first for 30 minutes to 60°C. and then for 24 hours to 100° C. This procedure yields an elastomerof excellent mechanical properties.

    ______________________________________                                        Tensile strength:  320 kp cm.sup.-2                                           Structural strength:                                                                             60 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         75                                                         ______________________________________                                    

EXAMPLE 13

197.4 g (0.1 mol) of the diamine produced in Example 3 and 18.5 gtoluylene diisocyanate are heated in a mould first for 30 minutes to 60°C. and then for 24 hours to 100° C. This procedure yields an elastomerof excellent mechanical properties.

    ______________________________________                                        Tensile strength:  280 kp cm.sup.-2                                           Structural strength:                                                                             44 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         82                                                         ______________________________________                                    

EXAMPLE 14

130.8 g of the diamine produced in Example 4 are reacted at 60°-70° C.with 18.5 g toluylene diisocyanate. After 15 minutes, the temperature israised to 90° C. under water jet vacuum. At this temperature, 5.9 gmelted 1,4-dichloro-3,5-diaminobenzene are added to the mixture and itis poured into a preheated mould. This procedure yields an elastomer ofexcellent mechanical properties.

    ______________________________________                                        Tensile strength:  310 kp cm.sup.-2                                           Structural strength:                                                                             45 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         86                                                         ______________________________________                                    

EXAMPLE 15

42.5 g (0.245 mol) toluylene diisocyanate (80% 2,4-isomer, 20%2,6-isomer) are added to 224 g (0.1 mol) of a compound of the formula Iwhich has been produced from 2,2-di(4-hydroxyphenyl)-propane, proyleneoxide and isatic acid anhydride, followed by stirring for 1 hour at 80°C. Then, 26.7 g 1,4-dichloro-3,5-diaminobenzene heated to 120° C. areadded and the reaction mixture is poured into a mould. It is heated for24 hour, whereupon an elastomer of the following properties is obtained:

    ______________________________________                                        Tensile strength:  285 kp cm.sup.-2                                           Structural strength:                                                                             46 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         96                                                         ______________________________________                                    

EXAMPLE 16

198.2 g (0.1 mol) of the compound specified in Example 4 to which 61.25g (0.245 mol) of 4,4-diisocyanato-diphenyl-methane have been added areheated under stirring for 1 hour to 80° C. Then,1,4-dichloro-3,5-diaminobenzene heated to 80° C. is added and themixture is poured into a mould. After heating for 24 hours, al elastomerof the following properties is obtained:

    ______________________________________                                        Tensile strength:  380 kp cm.sup.-2                                           Structural strength:                                                                             65 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         56                                                         ______________________________________                                    

EXAMPLE 17

209.4 g (0.1 mol) of the compound produced according to Example 9 and18.5 g toluylene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) aremixed, poured into a mould, and then heated for 30 minutes to 60° C. andfor 24 hours to 100° C. This procedure yields an elastomer of thefollowing properties:

    ______________________________________                                        Tensile Strength:  290 kp cm.sup.-2                                           Structural Strength:                                                                             50 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         76                                                         ______________________________________                                    

EXAMPLE 18

164.4 g (0.1 mol) of the compound produced according to Example 10 and18.5 g toluylene diisocyanate are heated in a mould for 30 minutes to60° C. and then for 24 hours to 100° C. This yields an elastomer ofexcellent mechanical properties.

    ______________________________________                                        Tensile strength:     300 kp cm.sup.-2                                        Structural strength:  56 kp cm.sup.-1                                         Shore hardness DIN 5305                                                                             80                                                      ______________________________________                                    

EXAMPLE 19

138.2 g of the compound produced according to Example 9 are reacted with18.5 g toluylene diisocyanate at 60°-70° C. After 15 minutes, thetemperature is raised to 90° C. under water jet vacuum. At thistemperature, 5.9 g melted 1,4-dichloro-3,5-diaminobenzene are added tothe mixture and it is poured into a preheated mould. This procedureyields an elastomer of excellent mechanical properties.

    ______________________________________                                        Tensile strength:  300 kp cm.sup.-2                                           Structural strength:                                                                             60 kp cm.sup.-1                                            Shore hardness DIN 53505                                                                         72                                                         ______________________________________                                    

The polymer compositions described herein and defined by the followingclaims can be used in the formation of vehicle tires of all types aswell as portions of vehicle tires such as plastic inserts for the chainsof tractor vehicles, plastic linings for wheels, such as the pulleys ofcable cars, plastic wheel rims for rail vehicles, conveyor belts,fasteners such as plastic pins and bolts as well as shoe soles.

We claim:
 1. Plastic materials produced according to the isocyanatepolyaddition process by reacting compounds having terminal amino groups,said compounds being of the general formula ##STR14## wherein z is aninteger of 2 to 4, X is oxygen or sulfur and R is a group of the formula

    --Y--[Ar-B].sub.k                                          (II)

wherein k stands for an integer of 1 to 4, Ar is an aromatic group, Ywhen k=1 is B and when k=2 is an alkylidene group having 1 to 5 carbonatoms and B represents a divalent polyalkylene ether group orpolyalkylene thioether group such as it is obtained by the removal ofthe hydroxyl or mercapto groups from a polyalkylene ether diol or apolyalkylene thioether dithiol, of a molecular weight of about 100 to15000, with a polyisocyanate.
 2. Plastic material according to claim 1,wherein a compound of the general formula I, wherein B stands for adivalent polyalkylene ether group or a polyalkylene thioether group suchas it is obtained by removal of the hydroxyl or mercapto groups from apolyalkylene ether diol or a polyalkylene thioether dithiol of amolecular weight of 500 to 3000, is employed.
 3. Plastic materialaccording to claim 1, wherein a compound of the general formula I,wherein Ar represents a p-phenylene group, is employed.
 4. Plasticmaterial according to claim 1, wherein a compound of the general formulaI, wherein Ar represents a diphenyl alkane group, is employed. 5.Plastic material according to claim 1, wherein a compound of the generalformula I, wherein Ar represents the diphenyl propane group, isemployed.
 6. Plastic material according to claim 1, wherein a compoundof the general formula I, wherein Ar represents a 1,5-naphthalene groupor a 1,4-naphthalene group, is employed.
 7. Plastic material accordingto claim 1, wherein a compound of the general formula I, wherein Bstands for a polyethylene ether group, is employed.
 8. Plastic materialaccording to claim 1, wherein a compound of the general formula I,wherein B stands for a polypropylene ether group, is employed. 9.Plastic material according to claim 1, wherein a compound of the generalformula I, wherein B stands for a polyalkylene ether group containingethylene ether groups and propylene ether groups, in any given sequence,is employed.
 10. Plastic material according to claim 1, wherein acompound of the general formula I, wherein B stands for a groupcontaining ether groups as well as thioether groups, is employed. 11.Plastic material according to claim 1, wherein a compound of the generalformula I, wherein B stands for a polyalkylene ether group derived fromtetrahydrofurane, is employed.
 12. Plastic material according to claim1, wherein a compound of the general formula I, wherein B stands for apolyalkylene ether group containing ethylene ether groups and alkyleneether groups derived from tetrahydrofurane, in any given sequence, isemployed.
 13. Plastic material according to claim 1, wherein a compoundof the general formula I, wherein B stands for a polyalkylene ethergroup containing alkylene ether groups derived from tetrahydrofurane,and propylene ether groups, in any given sequence, is employed. 14.Plastic material according to claim 1, wherein the compound of thefollowing formula is employed: ##STR15##
 15. Plastic material accordingto claim 1, wherein the compound of the following formula is employed:##STR16##
 16. Plastic material according to claim 1, wherein thecompound of the following formula is employed: ##STR17##
 17. Plasticmaterial according to claim 1, wherein the compound of the followingformula is employed: ##STR18##
 18. Plastic material according to claim1, wherein the compound of the following formula is employed: ##STR19##19. Plastic material according to claim 1, wherein the compound of thefollowing formula is employed: ##STR20##
 20. A vehicle tire formed fromthe plastic material defined in claim
 1. 21. A shaped article formedfrom the plastic material defined in claim 1.